CN102267943B - Method for preparing 5-chloro-8-hydroxyquinoline - Google Patents
Method for preparing 5-chloro-8-hydroxyquinoline Download PDFInfo
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- CN102267943B CN102267943B CN2011102152005A CN201110215200A CN102267943B CN 102267943 B CN102267943 B CN 102267943B CN 2011102152005 A CN2011102152005 A CN 2011102152005A CN 201110215200 A CN201110215200 A CN 201110215200A CN 102267943 B CN102267943 B CN 102267943B
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Abstract
The invention discloses a method for preparing 5-chloro-8-hydroxyquinoline and belongs to the technical field of chemistry. The 5-chloro-8-hydroxyquinoline is prepared from raw material components including 4-chloroonitrophenol, 4-chloroortho-aminophenol, glycerol and concentrated sulfuric acid according to a molar ratio of 4-chloroortho-aminophenol to 4-chloroonitrophenol of 1.6:3.2 and a molar ratio of glycerol to 4-chloroonitrophenol of 2.6:5.2 and a molar ratio of sulfuric acid to 4-chloroonitrophenol of 3:9. The method comprises: dripping sulfuric acid into the components under a condition that the temperature of the solvent is 100 to 170 DEG C; and under the sulfuric acid is dripped completely, promoting the reaction to complete by the following measures and removing part of water generated in reaction under vacuum, or removing part or all water byproduct of the reaction by using benzene, methylbenzene, paraxylene or chlorobenzene as an azeotropic water reducing agent. During after-reaction treatment, industrial concentrated hydrochloric acid is used in place of organic solvent to perform refining treatment to remove pigments and impurities from the product, and the product yield is increased. The method is mainly used for synthesizing cloquintocet-mexyl serving as a herbicide component and can also be used as an animal feed additive, a disinfectant and a metal preservative.
Description
Technical field
The present invention relates to chemical technology field, relate in particular to a kind of method of the 5-of preparation chloro-oxine.
Background technology
5-chloro-oxine is mainly used in synthetic herbicide component cloquintocetmexyl, and also as animal foodstuff additive, sterilizing agent and anticolodal, the preparation method of 5-chloro-oxine has multiple; Be seen in the synthetic technology document of report and disclosed 5-chloro-oxine and mainly contain: 1., use oxine to be raw material, use a large amount of glacial acetic acids to be solvent; Logical chlorine prepares 5-chloro-oxine; Yield is 52.7% (JP162066), and main by product is 5, the 7-dichloro-8-hydroxyquinoline..The shortcoming of this technology is that main raw material is expensive, and reaction preference is poor, and impurity is many; 2., use oxine to be raw material, prepare 5-chloro-oxine with the sulfuryl chloride chlorination, yield is 49% (JP162066).Shortcoming also is that raw material is expensive, poor selectivity, and yield is low; 3., with oxine, hydrochloric acid and ydrogen peroxide 50 are feedstock production 5-chloro-oxine, yield 78.2% [Ger. (east) .DD149859].Though yield increases, main raw material is expensive, causes total cost higher; 4., be the synthetic 5-chloro-oxine of raw material with 4-chlorine o-NP, 4-chlorine Ortho-Aminophenol, glycerine and sulfuric acid, be 59% [Radioisotopes, 1975,24 (7), 500-4] with the glycerine calculated yield.This raw materials technology is inexpensive, but yield is also on the low side.The reason that yield is low has 2 points: the one, react complete inadequately, and another is to use a large amount of organic solvents when making with extra care aftertreatment, loaded down with trivial details loss is big.
Summary of the invention
In order to overcome the deficiency of above-mentioned 4. technology, the invention provides a kind of method of the 5-of preparation chloro-oxine, utilize the prepared 5-chloro-oxine of this method, yield is high, and content is greater than 99%
The technical solution adopted for the present invention to solve the technical problems is:
A kind of method for preparing 5-chloro-oxine, its step is following: A disposes solvent, and the mol ratio of 4-chlorine Ortho-Aminophenol and 4-chlorine o-NP is 1.6: 3.2, and glycerine and 4-chlorine o-NP mol ratio are 2.6: 5.2,
Sulfuric acid and 4-chlorine o-NP mol ratio are 3: 9; B is synthetic, with above-mentioned component solvent and 100 ℃ of-170 ℃ of temperature condition down dropping sulfuric acid react and follow dehydration; C neutralization, reacted material neutralizes with alkali lye, after isolate 5-chloro-oxine bullion; D is refining, and neutralization back refinement treatment is carried out refinement treatment with industrial mineral acid replace organic solvent; E is dry, gets highly purified 5-chloro-oxine.
Glycerine, 4-chlorine o-NP, 4-chlorine Ortho-Aminophenol are dropped in the still, drip sulfuric acid and react.The mol ratio of 4-chlorine Ortho-Aminophenol and 4-chlorine o-NP is 1.6: 3.2.Glycerine and 4-chlorine o-NP mol ratio are 2.6: 5.2.Sulfuric acid and 4-chlorine o-NP mol ratio are 3: 9, and the sulfuric acid dropping temperature is 100 ℃ of-170 ℃ of degree, and optimum temps is 105 ℃-150 ℃.The reaction while dripping.Sulfuric acid drips complete, continues insulation reaction 1-10 hour, and holding temperature is 110 ℃-160 ℃.Between soak, take following measure to promote to react completely: to give vacuum and remove the water that produces in the part reaction; Or from benzene, toluene, p-Xylol is chosen any one kind of them in the chlorobenzene and is made the azeotropic dehydrating agent, and part is removed to the water of by-product in whole removal reactions, and the end back of anhydrating is steamed and is removed entrainment agent.Reaction finishes the back cooling, and adding 10% sodium hydroxide solution, to be neutralized to pH value be 7.Centrifuging obtains bullion.Bullion is dropped in the reaction kettle, and the water and the small amount of activated that add 5 times of bullion weight are filtered decolouring.Filtrating is gone in another reaction kettle.It is 7 that processing industry hydrochloric acid is neutralized to pH value.Cross and filter decolouring back bullion.The back bullion that will decolour drops in another still, adds decolouring back bullion weight 2-8 technical hydrochloric acid doubly and is heated to 60 ℃-110 ℃ and stirs 1 hour postcooling to room temperature after-filtration and get refined prod.Get finished product after the oven dry.
Remove the water of reaction by-product through part after, make reaction reach complete.Through selecting salt acid treating bullion for use, can farthest remove color impurities.Overcome in the past in the technology bullion with the refining repeatedly shortcoming repeatedly of organic solvent.Significantly reduced the loss of product in the refining last handling process, improved the total recovery of product, cost descends, and product appearance is to off-white color, and content is high.
Embodiment
Embodiment 1
In the 1000L reaction kettle, drop into 100 kilograms of 4-chlorine o-NPs, 173.7 kilograms of 4-chlorine Ortho-Aminophenols, 175 kilograms of glycerine stir and are warming up to 120 ℃, drip 410 kilograms of sulfuric acid, droplet finish in 150 ℃ of insulation reaction 3 hours.Deviate from 70 kg of water with vacuum between soak.Insulation reaction is cooled to 60 ℃ after finishing, and dripping 10% aqueous sodium hydroxide solution to pH value is 7.Centrifugal, filter cake drops in the 3000L still, adds 2200 kg of water, 200 kilogram of 32% technical hydrochloric acid, 15 kilograms of gacs, dissolving after-filtration.Filtrating is evacuated in another 3000L still, drips 30% liquid caustic soda and neutralizes for 233 kilograms, and is centrifugal.Filter cake is dropped in another 2000L still, add 1250 kilogram of 32% technical hydrochloric acid, stir centrifugal after 1 hour.
Filter cake is dropped in another 3000L still, add 2200 kilograms in water, drip 30% liquid caustic soda after the stirring and dissolving to PH most 7.Centrifugal rinsing dry 260 kilograms of products, HPLC purity 99.4%.
Embodiment 2:
In the 1000L reaction kettle, drop into 97 kilograms of 4-chlorine o-NPs, 145 kilograms of 4-chlorine Ortho-Aminophenols, 150 kilograms and 100 kilograms toluene of glycerine stir and are warming up to 105 ℃, drip 410 kilograms of sulfuric acid, droplet finish in 110 ℃ of-145 ℃ of insulation reaction 5 hours.Also steam with deviating from 65 kg of water between soak except that toluene.Insulation reaction is cooled to 60 ℃ after finishing, and dripping 10% aqueous sodium hydroxide solution to pH value is 7.Centrifugal, filter cake drops in the 3000L still, adds 1850 kg of water, 170 kilogram of 32% technical hydrochloric acid, 12 kilograms of gacs, dissolving after-filtration.Filtrating is evacuated in another 3000L still, drips 30% liquid caustic soda and neutralizes for 200 kilograms, and is centrifugal.Filter cake is dropped in another 2000L still, add 1100 kilogram of 32% technical hydrochloric acid, stir centrifugal after 1 hour.Filter cake is dropped in another 3000L still, add 1850 kilograms in water, drip 30% liquid caustic soda after the stirring and dissolving to PH most 7.Centrifugal rinsing dry 242 kilograms of products, HPLC purity 99.2%.
Embodiment 3
In the 1000L reaction kettle, drop into 97 kilograms of 4-chlorine o-NPs, 160 kilograms of 4-chlorine Ortho-Aminophenols, 150 kilograms of glycerine stir and are warming up to 120 ℃, drip 410 kilograms of sulfuric acid, droplet finish in 150 ℃ of insulation reaction 4 hours.Insulation reaction is cooled to 60 ℃ after finishing, and dripping 10% aqueous sodium hydroxide solution to pH value is 7.Centrifugal, filter cake drops in the 3000L still, adds 2050 kg of water, 160 kilogram of 32% technical hydrochloric acid, 20 kilograms of gacs, dissolving after-filtration.Filtrating is evacuated in another 3000L still, drips 30% liquid caustic soda and neutralizes for 187 kilograms, and is centrifugal.Filter cake is dropped in another 2000L still, add 770 kilograms of ethanol and 330 kg of water and 15 kilograms of gacs, the decolouring of heating for dissolving after-filtration, it is centrifugal that filtrating is cooled to 0 degree.Filter cake more once with 770 kilograms of ethanol and 330 kg of water and 15 kilograms of gacs dissolving decolourings, centrifugal dry 180 kilograms of products, HPLC purity 99.3%.
The above; Be merely embodiment of the present invention, but the protection domain of invention is not limited thereto, any those of ordinary skill in the art are in the technical scope that the present invention discloses; The variation that can expect easily or replacement all should be encompassed within the protection domain of invention.
Claims (1)
1. method for preparing 5-chloro-oxine, its step is following:
In the 1000L reaction kettle, drop into 100 kilograms of 4-chlorine o-NPs, 173.7 kilograms of 4-chlorine Ortho-Aminophenols, 175 kilograms of glycerine; Stirring is warming up to 120 ℃, drips 410 kilograms of sulfuric acid, drips to finish in 150 ℃ of insulation reaction 3 hours, deviates from 70 kg of water with vacuum between soak; Insulation reaction is cooled to 60 ℃ after finishing, and drips 10% aqueous sodium hydroxide solution to pH value and is 7, and is centrifugal; Filter cake drops in the 3000L still, adds 2200 kg of water, 200 kilogram of 32% technical hydrochloric acid, 15 kilograms of gacs; The dissolving after-filtration, filtrating is evacuated in another 3000L still, drips 30% liquid caustic soda and neutralizes for 233 kilograms, and is centrifugal; Filter cake is dropped in another 2000L still, add 1250 kilogram of 32% technical hydrochloric acid, stir centrifugal after 1 hour;
Filter cake is dropped in another 3000L still, add 2200 kilograms in water, dripping 30% liquid caustic soda after the stirring and dissolving is 7 to pH, centrifugal rinsing dry 260 kilograms of products, HPLC purity 99.4%.
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| CN106501412B (en) * | 2016-11-23 | 2019-04-16 | 太原理工大学 | A method of it is measured by high efficiency liquid phase chromatographic analysis method and prepares o-aminophenol yield using o-nitrophenol |
| CN108610288B (en) * | 2016-12-09 | 2020-11-24 | 利尔化学股份有限公司 | Preparation method and purification method of 5-chloro-8-hydroxyquinoline |
| CN106986824A (en) * | 2017-05-08 | 2017-07-28 | 宜兴市宏博精细化工有限公司 | A kind of 8 oxyquinoline preparation facilities |
| CN107954929A (en) * | 2017-12-24 | 2018-04-24 | 抚州市萨弗隆化工有限公司 | A kind of process units of 8-hydroxyquinoline halides |
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| CN1405155A (en) * | 2002-11-04 | 2003-03-26 | 卢宪春 | 5-chloro-8-hydroxyquinoline preparation method |
| CN101591290A (en) * | 2009-06-19 | 2009-12-02 | 夏士朋 | The back-end production process of synthesis of quinoline and derivative thereof |
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